Different Patterns of Pd-Promoted C-H Bond Activation in (Z)-4-Hetarylidene-5(4H)-oxazolones and Consequences in Photophysical Properties

This work aims to amplify the fluorescence of (Z)-4-hetarylidene-5(4H)-oxazolones 1 by suppression of the hula-twist non-radiative deactivation pathway by C^N-orthopalladation of the 4-hetarylidene ring. Different (Z)-4-hetarylidene-2-phenyl-5(4H)-oxazolones, 1a–1c, prepared by the Erlenmeyer–Plöchl...

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Autores: Martínez, Miguel, Dalmau, David, Crespo, Olga, García-Orduña, Pilar, Lahoz, Fernando, Martín, Antonio, Urriolabeitia, Esteban P.
Tipo de recurso: artículo
Estado:Versión publicada
Fecha de publicación:2024
País:España
Institución:Universidad de Zaragoza
Repositorio:Zaguán. Repositorio Digital de la Universidad de Zaragoza
OAI Identifier:oai:zaguan.unizar.es:145634
Acceso en línea:http://zaguan.unizar.es/record/145634
Access Level:acceso abierto
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spelling Different Patterns of Pd-Promoted C-H Bond Activation in (Z)-4-Hetarylidene-5(4H)-oxazolones and Consequences in Photophysical PropertiesMartínez, MiguelDalmau, DavidCrespo, OlgaGarcía-Orduña, PilarLahoz, FernandoMartín, AntonioUrriolabeitia, Esteban P.This work aims to amplify the fluorescence of (Z)-4-hetarylidene-5(4H)-oxazolones 1 by suppression of the hula-twist non-radiative deactivation pathway by C^N-orthopalladation of the 4-hetarylidene ring. Different (Z)-4-hetarylidene-2-phenyl-5(4H)-oxazolones, 1a–1c, prepared by the Erlenmeyer–Plöchl method, have been studied. The orthopalladation of (Z)-2-phenyl-4-(5-thiazolylmethylene)-5(4H)-oxazolone (1a) takes place by C-H bond activation of the H4 of the heterocycle and C^N-chelation, giving the dinuclear trifluoroacetate derivative 2a. By further metathesis of bridging ligands in 2a, complexes containing the orthometalated oxazolone and a variety of ligands 3a–5a, were prepared. The study of the photophysical properties of 1a–5a shows that the bonding of the Pd metal to the 4-hetaryliden-5(4H)-oxazolone does not promote, in these cases, an increase in fluorescence. Interestingly, the orthopalladation of (Z)-2-phenyl-4-(4-thiazolylmethylene)-5(4H)-oxazolone (1b) gives orthopalladated 2b, where the incorporation of the Pd to the oxazolone takes place by C-H bond activation of the ortho-H2 of the 2-phenyl group, ring opening of the oxazolone heterocycle and simultaneous N,N-bonding of the N atoms of the thiazole ring and the generated benzamide fragment. This N^N^C-tridentate dianionic bonding mode is obtained for the first time in oxazolones. Despite a similar lock of the hula-twist deactivation, 2b does not show fluorescence.2024info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionapplication/pdfhttp://zaguan.unizar.es/record/145634reponame:Zaguán. Repositorio Digital de la Universidad de Zaragozainstname:Universidad de ZaragozaInglésinfo:eu-repo/grantAgreement/ES/DGA/E07-23Rinfo:eu-repo/grantAgreement/ES/DGA/E17-23Rinfo:eu-repo/grantAgreement/ES/MICINN AEI/PID2022-136861NB-I00info:eu-repo/grantAgreement/ES/MICINN/PID2019-106394GB-I00info:eu-repo/grantAgreement/ES/MICINN/PID2021-122869NB-I00info:eu-repo/semantics/openAccessoai:zaguan.unizar.es:1456342026-05-29T13:59:51Z
dc.title.none.fl_str_mv Different Patterns of Pd-Promoted C-H Bond Activation in (Z)-4-Hetarylidene-5(4H)-oxazolones and Consequences in Photophysical Properties
title Different Patterns of Pd-Promoted C-H Bond Activation in (Z)-4-Hetarylidene-5(4H)-oxazolones and Consequences in Photophysical Properties
spellingShingle Different Patterns of Pd-Promoted C-H Bond Activation in (Z)-4-Hetarylidene-5(4H)-oxazolones and Consequences in Photophysical Properties
Martínez, Miguel
title_short Different Patterns of Pd-Promoted C-H Bond Activation in (Z)-4-Hetarylidene-5(4H)-oxazolones and Consequences in Photophysical Properties
title_full Different Patterns of Pd-Promoted C-H Bond Activation in (Z)-4-Hetarylidene-5(4H)-oxazolones and Consequences in Photophysical Properties
title_fullStr Different Patterns of Pd-Promoted C-H Bond Activation in (Z)-4-Hetarylidene-5(4H)-oxazolones and Consequences in Photophysical Properties
title_full_unstemmed Different Patterns of Pd-Promoted C-H Bond Activation in (Z)-4-Hetarylidene-5(4H)-oxazolones and Consequences in Photophysical Properties
title_sort Different Patterns of Pd-Promoted C-H Bond Activation in (Z)-4-Hetarylidene-5(4H)-oxazolones and Consequences in Photophysical Properties
dc.creator.none.fl_str_mv Martínez, Miguel
Dalmau, David
Crespo, Olga
García-Orduña, Pilar
Lahoz, Fernando
Martín, Antonio
Urriolabeitia, Esteban P.
author Martínez, Miguel
author_facet Martínez, Miguel
Dalmau, David
Crespo, Olga
García-Orduña, Pilar
Lahoz, Fernando
Martín, Antonio
Urriolabeitia, Esteban P.
author_role author
author2 Dalmau, David
Crespo, Olga
García-Orduña, Pilar
Lahoz, Fernando
Martín, Antonio
Urriolabeitia, Esteban P.
author2_role author
author
author
author
author
author
description This work aims to amplify the fluorescence of (Z)-4-hetarylidene-5(4H)-oxazolones 1 by suppression of the hula-twist non-radiative deactivation pathway by C^N-orthopalladation of the 4-hetarylidene ring. Different (Z)-4-hetarylidene-2-phenyl-5(4H)-oxazolones, 1a–1c, prepared by the Erlenmeyer–Plöchl method, have been studied. The orthopalladation of (Z)-2-phenyl-4-(5-thiazolylmethylene)-5(4H)-oxazolone (1a) takes place by C-H bond activation of the H4 of the heterocycle and C^N-chelation, giving the dinuclear trifluoroacetate derivative 2a. By further metathesis of bridging ligands in 2a, complexes containing the orthometalated oxazolone and a variety of ligands 3a–5a, were prepared. The study of the photophysical properties of 1a–5a shows that the bonding of the Pd metal to the 4-hetaryliden-5(4H)-oxazolone does not promote, in these cases, an increase in fluorescence. Interestingly, the orthopalladation of (Z)-2-phenyl-4-(4-thiazolylmethylene)-5(4H)-oxazolone (1b) gives orthopalladated 2b, where the incorporation of the Pd to the oxazolone takes place by C-H bond activation of the ortho-H2 of the 2-phenyl group, ring opening of the oxazolone heterocycle and simultaneous N,N-bonding of the N atoms of the thiazole ring and the generated benzamide fragment. This N^N^C-tridentate dianionic bonding mode is obtained for the first time in oxazolones. Despite a similar lock of the hula-twist deactivation, 2b does not show fluorescence.
publishDate 2024
dc.date.none.fl_str_mv 2024
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/publishedVersion
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv http://zaguan.unizar.es/record/145634
url http://zaguan.unizar.es/record/145634
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv info:eu-repo/grantAgreement/ES/DGA/E07-23R
info:eu-repo/grantAgreement/ES/DGA/E17-23R
info:eu-repo/grantAgreement/ES/MICINN AEI/PID2022-136861NB-I00
info:eu-repo/grantAgreement/ES/MICINN/PID2019-106394GB-I00
info:eu-repo/grantAgreement/ES/MICINN/PID2021-122869NB-I00
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv application/pdf
dc.publisher.none.fl_str_mv
publisher.none.fl_str_mv
dc.source.none.fl_str_mv reponame:Zaguán. Repositorio Digital de la Universidad de Zaragoza
instname:Universidad de Zaragoza
instname_str Universidad de Zaragoza
reponame_str Zaguán. Repositorio Digital de la Universidad de Zaragoza
collection Zaguán. Repositorio Digital de la Universidad de Zaragoza
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